Presented below is background information on certain aspects of the present invention as they may relate, to technical features referred to in the detailed description, but not necessarily described in detail. The discussion below should not be construed as an admission as to the relevance of the information to the claimed invention or the prior art effect of the material described.
The search for a membrane for use in fluid separation applications that combines high selectivity with high flux continues. Current perfluoropolymer membranes, such as those made from Hyflon® AD (Solvay), Teflon® AF (Du Pont), Cytop® (Asahi Glass), and variants thereof, have excellent chemical resistance and stability. We reported earlier, in U.S. Pat. No, 6,361,583, membranes that are made from glassy polymers or copolymers, including Hyflon® AD, and arc characterized by having repeating units of a fluorinated, cyclic structure. In general, the ring structures in these materials frustrate polymer chain packing yielding amorphous polymers with relatively high fluid permeability. These developed membranes are also more resistant to plasticization by hydrocarbons than prior art membranes and are able to recover from accidental exposure to liquid hydrocarbons.
It is known that copolymerization of fluorinated cyclic monomers with tetrafluoroethylene (TFE) enhances the chemical resistance and physical rigidity of membranes. TFE is also known to improve processability and has the effect of lowering fluid permeability and increasing size selectivity in Hyflon® AD and Teflon® AF. Therefore, combinations of TFE with other monomer units, in particular perfluorinated dioxoles, such as in Teflon® AF and Hyflon® AD, that result in overall amorphous, yet rigid, highly fluorinated, copolymers are useful for industrial membrane applications. However, a drawback to these membranes is that their selectivities are relatively low for a number of separations of interest, including H2/CH4, He/CH4, CO2/CH4, and N2/CH4.
Other than the commercially available perfluoropolymers, there is very limited fluid transport data available for fully fluorinated polymers. Paul and Chio, “Gas permeation in a dry Nation membrane,” Industrial & Engineering Chemistry Research, 27, 2161-2164 (1988), examined gas transport in dry Nation® (an ionic copolymer of TFE and sulfonated perfluorovinyl ether) and found relatively high permeabilities and selectivities for several gas pairs (He/CH4, He/H2, and N2/CH4) compared to conventional hydrocarbon-based polymers considered for membrane applications, Nafion® and related ionic materials are used to make ion exchange membranes for electrochemical cells and the like. Because of their high cost and need for carefully controlled operating conditions, such as adjusting the relative humidity of the feed gas to prevent polymer swelling and loss of performance, these ionic membranes are not suitable for industrial gas separations,
U.S. Pat. No. 5,051,114, to DuPont, discloses the testing of poly-[perfluoro-2-methylene-4-methyl-1,3-dioxolane] for use in a membrane for gas separation. The results indicated that this material exhibited gas permeabilities 2.5 to 40 times lower as compared to dipolymer membranes of perfluoro-2,2-dimethyl-1,3-dioxole and TFE, but had higher selectivities. Also disclosed are copolymers of perfluoro-2,2-dimethyl-1,3-dioxole and either tetrafluoroethylene, perfluoromethyl vinyl ether, vinylidene fluoride, or chlorotrifluoroethylene.
Recently, there have been reports of new non-ionic amorphous perfluoropolymers. U.S. Pat. Nos. 7,582,714; 7,635,780; 7,754,901; and 8,168,808, all to Yoshiyuki Okamoto, disclose compositions and processes for making dioxolane derivatives.
Yana et al., “Novel Amorphous Perfluorocopolymeric System: Copolymers of Perfluoro-2-methylene-1,3-dioxolane Derivatives,” Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 1613-1618 (2006), and Okamoto et al., “Synthesis and properties of amorphous perfluorinated polymers,” Chemistry Today, vol. 27, n. 4, pp. 46-48 (July-August 2009), disclose the copolymerization of two dioxolane derivatives, perfluorotetrahydro-2-methylene-furo[3,4,-d][1,3]dioxolane and perfluoro-2-methylene-4-methoxymethyl-1,3-dioxolane. The copolymers were found to be thermally stable, have low refractive indices, and high optical transparency from UV to near-infrared, making them ideal candidates for use in optical and electrical materials.
Liu et al., “Free-Radical Polymerization of Dioxolane and Dioxane Derivatives: Effect of Fluorine Substituents on the Ring Opening Polymerization,” Journal of Polymer Science; Part A: Polymer Chemistry, Vol. 42, 5180-5188 (2004), discloses the synthesis of partially-and fully-fluorinated dioxolane and dioxane monomers that may be used in materials for optical fiber applications.
Mikes et al., “Synthesis and Characterization of Perfluoro-3-methylene-2,4,-dioxabicyclo[3,3,0]octane: Homo-and Copolymerization with Fluorovinyl Monomers,” J Polym Sci Part A: Polym Chem, 47: 6571-6578 (2009), discloses copolymers of perfluoro-3-methylene-2,3-dioxabicyclo-[3,3,0]octane with chlorotrifluoroethylene (CTFE), perfluoropropyl vinyl ether, perfluoromethyl vinyl ether, and vinylidene fluoride for use in a variety of applications.
Boshet and Ameduri “(Co)polymers of Chlorotrifluoroethylene: Synthesis, Properties, and Applications,” Chem. Rev, 2014, 114, 927-980, discloses copolymers of chlorotrifluoroethylene and perfluoro-3-methylene-2,3-dioxabicyclo-[3,3,0]octane for use in optical fiber applications.
Paul and Yampol'ski, “Polymeric Gas Separation Membranes,” CRC Press, pp. 416-419 (1994), discloses polymer membranes investigated by Asahi Glass Co. that contain a copolymer of tetrafluoroethylene and perfluoro-2-methylene-4-methyl-1,-3-dioxolane. However, no gas separation data is presented.
U.S. Pat. No. 9,079,138 to Nemser et al., discloses a method for making fluorinated polymeric membranes comprising, for example, a copolymer of perfluoro-2-methylene-4-methyl-1,3-dioxolane and a fluorovinyl monomer, which can be used for separating liquid components under nanofiltration type operating conditions. These membranes have a high transmembrane flux, which is unsuitable for gas separation:
Ezhov, “Investigation of Permeability of Fluorine and Certain Gases through Nonporous Fluorine-Resistant Polymers,” Petroleum Chemistry, 2014, Vol. 54, No. 8, pp. 608-611, and “Permeability of Fluorine and Some Other Fluorine-Containing Gases Through Nonporous Fluorine-stable Copolymers,” Atomic Energy, 2011, Vol. 110, No. 3, pp. 173-175, disclose the separation of certain fluorinated gases using thick films (30-100 μm) made of copolymers of vinylidene fluoride and perfluoro-2-methylene-4-methyl-1,3-dioxolane and perfluoro-2-methylene-1,3-dioxolane.
U.S. PGPUB 2012/0190091 to Huang et al. discloses a method for dehydrating organic/water solutions using a membrane having a selective layer firmed from highly fluorinated monomers, including copolymers of dioxolanes and fluorinated ethers and ethylene. However, no specific dioxolanes are disclosed.
To date, however, we are unaware of any published data reporting fluid separation performances of membranes made by copolymerizing perfluorodioxolane monomers with the fluorovinyl monomers as described herein.